Chemical manufacture



Patented Mar. 7, 1950 mass? UNITED 'l' NT OFFICE EHEMIGAL MANUFACTURE Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mm,

assignors to Petrolite Corporation, Ltd, Wilmington, Del, a corporation of Delaware No Drawing. Application February-16, 1948, Serial No. 8,724. In Venezuela March 7, 1947 18 Claims.

This invention relates to processes and procedures particularly adapted for preventing, breaking, or resolving emulsions .oi the water-in-oil type, and particularly petroleum emulsions. It is a continuation-impart of co-pending applications Serial Nos. 518,666 and 518,661. both filed January 17, 1944; Serial Nos. 666,817 and 666,821, both filed May 2, 1946; Serial Nos. 666,818 and 666,816, filed May 2, 1946; Serial Nos. 727,282 and 727,283, both filed February 7, 1947; Serial Nos. 751,610 and 751,605, filed May 31, 1947; and Serial No. 751,611, filed May 31, 1947, all now abandoned.

New chemical products or compounds, as well as the application of such chemical compounds, products, and the like, in various other arts and industries, along with methods for manufacturillg said new chemical. products or compounds which are of outstanding value in demulsification, described herein are described and claimed in our co-pending applications, Serial Nos. 751,- 623 and 751,620 filed May 31, 1947, both now abandoned, and also our co-pending application, Serial No. 8,725 filed February 16, 1948, as well as our co-pending applications, Serial No. 8,731 filed February 16, 1948, and Serial No. 42,134 filed August 2, 1948. Attention is also directed to our aforementioned co-pending application Serial No. 751,611 filed May 31, 1947.

Our invention provides an economical and rapid process for resolving petroleum emulsions of the water-in oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprises 'fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

It also providesan economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil, relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned are of significant value in removing impurities, particularly inorganic salts from pipeline oil.

Demulsification as contemplated in the present application includes the preventive ste of commingling the demulsifier with an aqueous component which would or might subsequently become either phase of the emulsion in the absence of such precautionary measure. Similarly, such demulsifier may be mixed with the hydrocarbon component J In our r b-pending applications above referred to we have described certain new products or tion, Serial No. 751,619, filedMay 31, 1947 (abancompositions of matter which are of unusual value in certain industrial applications requiring the use of products or compounds showing surface activity. We have found that if solventsoluble resins are prepared from difunctional (di reactive) phenols in which one of the reactive ,(0 or p) positions of the phenol is substituted byan atom or radical which, if containing carbon, does not have more than 24 carbon atoms, in the substantial absence of trifunctional phenols, and aldehydes having not over 8 carbon atoms, subsequent oxyalkylation, and specifically oxyethylation, yields products of unusual value for. demulsification purposes provided that oxyalkylation is continued to the degree that hydrophile properties are imparted to the compound. By substantial absence of trifunctional henols, we mean that such materials may bepresent only in amounts so small that they do not interfere In experiments following conventional procedure using an acid catalyst in which we have included triiunctional phenols in amounts of from 3% to about 1% or somewhat less, based on the difunctional phenols, we have encountered difiiculties in preparing oxyalkylated derivatives of the type useful in the practice of this invention.

Attention is directed to ten co-pending applications:

(1) In respect to the use of demulsifying agents of the kind above described with the proviso that the hydrocarbon substitutent in the phenolic nucleus has 4 to 8 carbon atoms, we refer to our copending application for patent, Serial No. 727,- 282 filed February 7, 1947 (abandoned).

(2) In respect to the same products as new compositions or as new products valuable for various purposes in addition to demulsification, attention is directed to our co-pending applicadoned).

(3) In respect to the use of .demulsifying agents of the kind above described with. the proviso that the hydrocarbon substituent in the phenolic nucleus has 9 to 18 carbon atomsrwe (4) In respect to the same products as new compositions or as new products. valuable for various purposes in additi' ato demulsification,

3 attention is directed to our co-pending application, Serial No. 751,618 filed May 31, 1947 (abandoned).

(5) In respect to the use of demulsifying agents of the kind described, with the proviso that the hydrocarbon substituent in the phenolic nucleus has at least 2 and not more than 3 carbon atoms, we refer to our copending application for patent, Serial No. 751,606 filed May 31, 1947 (abandoned) (6) In respect to the same products as new compositions or as new products valuable for various purposes in addition to dernulsification, attention is directed to our co-pending application, Serial No. 751,617 filed May 31, 1947 (abandoned).

(7) In respect to the use of demulsifying agents which may be derived from phenolic reactants enumerated in the preceding categories, one may additionally employ as phenolic reactants cresols, xylenols, and substituted phenols in which the substituent has 19 to 24 carbon atoms. In connection with these compounds, particularly for use as demulsifying agents, attention is directed to our co-pending application, Serial No. 751,610 filed May 31, 1947 (abandoned) (8) In respect to the same products as new compositions or as new products valuable for various purposes in addition to demulsification, attention is directed to our co-pending application, Serial No. 751,623, filed May 31, 1947 (aban doned).

(9) In respect to the use of demulsifying agents of the kind described, with the proviso that the hydrocarbon substituent in the phenolic nucleus has at least 2 and not more than 24 carbon atoms, and with particular reference to mixtures in which phenols, having 4 to 8 carbon atoms in the substituent position, are mixed with phenols having 2 to 3 or 9 to 24 carbon atoms, reference is made to our co-pending application, Serial No. 8,728, filed February 16, 1948.

(10) In respect to the same products as new compositions or as new products valuable for various purposes in addition to demulsification, attention is directed to our co-pending application, Serial No. 8,729, filed February 16, 1948.

With respect to thermoplastic phenol-aldehyde resins from difunctional phenols, it is well known that the substituent which makes the phenol difunctional need not be a hydrocarbon radical but may bean atom, such as chlorine or bromine, or may be a radical which, in addition to having carbon and hydrogen present, may also have oxygen, or nitrogen or both. Well known examples are resins prepared from chlorinated phenols, from salicylic acid, from para-hydroxybenzoic acid, from esters of such carboxylic acids as methylsalicylate, from phenols in which the substituent in the 2,4,6 position is a hydroxyalkyl radical, a ketone radical, an aminoalcohol radical, a chlorinated hydrocarbon radical, etc. Of particular interest are phenols where R is carboalkoxy (carbalkoxy) such as carbomethoxy, carbethoxy, etc. Thus, the instant application is concerned with the use of compounds derived from phenolic resins in which the phenol is substituted in the 2,4,6 position, including the valuable class where the substituent radical in the phenolic nucleus which renders the phenol difunctional is not a hydrocarbon radical but is of a different type.

One useful type of compound herein employed may be exemplified in an idealized simplification inth'e following formula:

which, in turn, is considered a derivative of the fusible, organic solvent-soluble resin polymer:

In these formulas n represents a numeral varying from 1 to 13 or even more provided that the parent resin is fusible and organic solvent-soluble; n represents a numeral varying from 1 to 20 with the proviso that the average value of n be at least 2; and R is a substituent atom or radical, and if a radical containing carbon, does not have more than 24 carbon atoms. These numerical values of n and n" are, of course, on a statistical basis.

The present invention involves the use, as a demulsifier, of a hydrophile oxyalkylated 2,4,6 (1. e. 2,4 or 6) substituted monocyclic phenol-C1 to C3 aldehyde resin in which the ratio of oxy alkylene groups to phenolic nuclei is at least 2:1 and the alkylene radicals of the oxyalkylene groups are ethylene, propylene, butylene, hydrcxy propylene or hydroxy butylene, corresponding to the alpha-beta 'alkylene oxides, ethylene oxide, alpha-beta propylene oxide, alpha-beta butylene oxide, glycide and methylglycide.

One may employ products derived from resins obtained with the use of mixtures of phenols, for instance, mixtures of cresols and other hydrocarbon substituted phenols, or mixtures in which all the phenols are hydrocarbon substituted, or mixtures of phenols in which the substituent is other than hydrocarbon, or mixtures in which some of the phenols are substituted by a hydrocarbon, or mixtures in which some of the phenols are substituted by a hydrocarbon radical and others are not. Some of these mixtures will be illustrated subsequently.

More particularly, the present invention involves the use as a demulsifier of a compound having the following characteristics:

(1) Essentially a polymer, probably linear but not necessarily so, having at least 3 and preferably not over 15 or 20 phenolic or structural units. It may have more, as previously stated.

(2) The parent resin polymer being fusible and organic solvent-soluble as hereinafter described.

(3) The parent resin polymer being free from cross-linking or structure which cross-links during the heating incident to the oxyalkylation procedure to an extent sufiicient to prevent the possession of hydrophile or sub-surface-active or surface-active properties by the oxyalkylated resin. Minor proportions of trifunctional phenols sometimes present in commercial phenols are usually harmless.

(4) Each allcyleneoxy group is introduced at the phenolic hydroxyl position except possibly in an exceptional instance where a stable methylol group has been formed by virture of resin manufacture in presence of an alkalinecatalyst, and in instances in which the substituent has a labile or reactive hydrogen atom, as in resins derived from salicylic acid, which is not suitablyblocked prior to oxyalkylation. Occurrence of a stable methylol radical is the exception rather than the tion is presumably due to steric hindrance. Needless to say, one can use a mixture of two or more aldehydes although usually this has no advantage.

Resins of the kind which are used as intermediates for the compounds used in the practice of this invention are obtained with the use of acid catalysts or alkaline catalysts, or Without the use of any catalyst at all. Among the useful alkaline catalysts are ammonia, amines, and quaternary ammonium bases. It is generally accepted that when ammonia and amines are employed as catalysts they enter into the condensation reaction and, in fact, may operate by initial combination with the aldehydic reactant. The compound hexamethylenetetramine illustrates such a combination. In light of these various reactions it becomes difficult to present any formula which would depict the structure of the various resins prior to oxyalkylation. More will be said subsequently as to the difference between the use of an alkaline catalyst and an acid catalyst; even in the use of an alkaline catalyst there is considerable evidence to indicate that the products are not identical where different basic materials are employed. The basic materials employed include not only those previously enumerated but also the hydroxides of the alkali metals, hydroxides of the alkaline earth metals, salts of strong bases and weak acids such as sodium acetate, etc.

Suitable phenolic reactants include the following: paraand ortho-cresol; paraand ortho-ethyl-phenol; 3-methyl-4-ethyl-phenol; 3- methyllpropyl-phenol; 2 ethyl 3 methylphenol; 2-propyl-3-methyl-phenol; paraand ortho-propyl-phenol; para-tertiary-butylphenol; para-secondary-butyl-phenol; para-tertiary-amyl-phenol; para-secondary-amyl-phenol; para-tertiary-hexyl-phenol; para-isooctylphenol; ortho-phenyl-phenol; para-phenyl-phenol; thymol; ortho-benzyl-phenol; para-benzylphenol; para-cycloheXyl-phenol; para-tertiarydecyl-phenol; para-dodecyl-phenol; para-tetradecyl-phenol; para octadecyl-phenol; para-nonyl-phenol; para menthyl phenol; para-eicosanyl-phenol; para-docosanyl-phenol; paratetracosanyl-phenol; para-beta-naphthyl-phenol; para-alpha-naphthyl-phenol; para-pentadecyl-phenol; that of the formula in which R is C9H19 to C13H2'1; paraand orthocetyl-phenols; para-cumyl-phenol; phenols of the formula in which R1 represents a straight chain hydrocarbon radical containing at least 7 carbon atoms and R2 and R3 represent hydrocarbon radicals the total number of carbon atoms attached to the tertiary carbon being at least 11 and phenols of the formula.

in which R1 represents an alkyl hydrocarbon radical containing at least 7 carbon atoms in a straight chain and R2 represents an alkyl hydrocarbon radical containing at least 2 carbon atoms, the total number of carbon atoms in R1 and R2 being at least 11; the alkyl salicylates, including methyl salicylate, butyl salicylate, amyl salicylate, octyl salicylate, nonyl salicylate, dodecyl salicylate; benzyl salicylate, cyclohexyl salicylate, oleyl salicylate, styryl salicylate, phenoxy ethyl salicylate; p-hydroxy-ethyl-benzoate; salicylic acid; p-chlorophenol; o-chlorophenol; oand p-dimethylaminomethyl-phenol; p-pentenyl-phenol; guaiacol; catechol; p-phenoxyphenol p-hydroxybenzophenone; hydroXyphenylheptadecyl ketone; hydroxy-phenylheptadecenyl ketone; hydroxyphenylundecyl ketone; and the corresponding ortho-para substituted meta-cresols and 3,5-xylenols.

For convenience, the phenol has previously been referred to as monocycic in order to differentiate from fused nucleus polycyclic phenols, such as substituted naphthols. Specifically, monocyclic is limited to the nucleus in which the hydroxyl radical is attached. Broadly speaking, where a substituent is cyclic, particularly aryl, obviously in the usual sense such phenol is actually polycyclic although the phenolic hydroxyl is not attached to a fused polycyclic nucleus. Stated another way, phenols in which the hydroxyl group is directly attached to a condensed or fused polycyclic structure, are excluded. This matter, however, is clarified by the following consideration. The phenols herein contemplated for reaction may be indicated by the following formula:

in which R is selected from the class consisting of hydrogen atoms and substituent radicals, which, if hydrocarbon, have not more than 24 carbon atoms, with the proviso that one occurrence of R is the substituent and the other two occurrences are hydrogen atoms, and with the further provision that one or both of the 3 and 5 positions may be methyl substituted. The above formula possibly can be restated more conveniently in the following manner, to wit, that the phenol employed is of the folloWing formula, with the proviso that R is a substituent located in the 2,4,6 position, again with the provision as to 3 or 3,5 methyl substitution. This is conventional nomenclature, numbering the various positions in the usual clockwise manner, beginning with the hydroxyl position as one:

ll. mediate is employed to mean a stage having 6 or 7 units or even less. In the appended claims we have used low-stage to mean 3 to 7 units based on average molecular weight.

The molecular weight determinations, of course, require that the product be completely soluble in the particular solvent selected as, for

instance, benzene. The molecular Weight determination of such solution may involve either the freezing point as in the cryoscopic method, or, less conveniently perhaps, the boiling point in an ebullioscopic method. The advantage of the ebullioscopic method is that, in comparison with the cryoscopic method, it is more apt to insure complete solubility. One such common method to employ is that of Menzies and Wright (see J. Am. Chem. Soc. 43, 2309 and 2314 (1921)). Any suitable method for determining molecular weights will serve, although almost any procedure adopted has inherent limitations. A good method for determining the molecular weights of resins, especially solvent-soluble resins, is the cryoscopic procedure of Krumbhaar which employs diphenylamine as a solvent (see Coating and Ink Resins, page 157, Reinhold Publishing Co. 1947).

Subsequent examples will illustrate the use of an acid catalyst, an alkaline catalyst, and no catalyst. As far as resin manufacture per se is concerned, we prefer to use an acid catalyst, and particularly a mixture of an organic sulfo-acid and a mineral acid, along with a suitable solvent, such as xylene, as hereinafter illustrated in detail. However, we have obtained products from resins obtained by use of an alkaline catalyst which were just as satisfactory as those obtained employing acid catalysts. Sometimes a combination of both types of catalysts is used in different stages of resinification. Resins so obtained are also perfectly satisfactory.

In numerous instances the higher molecular weight resins, i. e., those referred to as highstage resins, are conveniently obtained by subjecting lower molecular weight resins to vacuum distillation and heating. Although such procedure sometimes removes only a modest amount or even perhaps no low polymer, yet it is almost certain to produce further polymerization. For instance, acid catalyzed resins obtained in the usual manner and having a molecular weight indicating the presence of approximately 4 phenolic units or' thereabouts may be subjected to such treatment, with the result that one obtains a resin having approximately double this molecular weight. The usual procedure is to use a secondary step, heating the resin in the presence or absence of an inert gas, including steam, or by use of Vacuum.

We have found that under the usual conditions of resinification employing phenols of the kind here described there is little or no tendency to form binuclear compounds, 1. e., dimers resulting from the combination, for example, of two moles of a phenol and one mole of formaldehyde, particularly where the substituent is a hydrocarbon radical and contains 4 or 5 carbon atoms. Where the substituent is hydrocarbon and contains 9 carbon atoms or more there is an increased tendency to form a measurable amount of dimers. The cogeneric formation of a relatively small amount of dimers is unimportant and there is no reason to separate the dimers prior to oxyalkylation and use. Among the phenomena observed as a hydrocarbon substituent increases in size are the following:

(1) There is a tendency to form dimers, even when molar equivalents, or an excess of an aldehyde is used. This is probably related to one or more of the following: (a) decreased reactiveness or sluggishness due to theincreased size of the reactant; (b) statistically less opportunity for reaction because the point of reaction, the reactive hydrogen atom, is diluted through greater molecular area or space; (0) the structure as such may afford decreased opportunity for reaction.

(2) There is an increased tolerance toward trifunctional phenols.

(3) Increasing the size of the side chain with a hydrocarbon substituent increases the carbonoxygen ratio of the finished resin and ultimately causes greater solubility in hydrocarbon solvents.

Where the substituent is hydrocarbon and has three carbon atoms or less, there is little tendency to form dimers, but certain differences in behavior as compared with phenols having higher hydrocarbon substituents become significant and noticeable. Thus, they have a decreased tolerance toward trifunctional phenols, are more highly reactive, the carbon-oxygen ratio of the finished resin becomes less, ultimately causing decreased solubility in hydrocarbon solvents, and the tendency to form resins which harden, cure, or cross-link even though the phenol be difunctional increases.

Resins having substituents containing carbon, oxygen and hydrogen in general exhibit behavior paralleling that of the hydrocarbon-substituted phenol resins, in that if the substituent has a hydrocarbon radical of substantial size, as, for example, in dodecyl salicylate, the behavior of the resin tends to be similar to that of one obtained from a phenol with a higher hydrocarbon substituent, while if the substituent contains no such group, as in salicylic acid and methyl salicylate resins, the behavior tends to be similar to that of the resins derived from phenols having lower hydrocarbon substituents. Resins with substituents such as chlorine obtained, for example, from orthoor para-chlorophenol, tend to behave like resins derived from cresols.

The substituted dihydroxy diphenyl methanes, i. e., dimers obtained from substituted phenols and aldehydes, are not resins as that term is used herein.

One need not use a single phenolic reactant, as mixtures of phenolic reactants give resins which are well adapted for the preparation of products used in the practice of the invention, and, in many cases, products obtained from mixtures of different phenolic reactants have advantages, either from the standpoint of production cost or demulsification effectiveness. Thus, the cresols, the ethyl phenols and the propyl phenols (difunctional in all cases) are obtainable at a cost of 50 to 60% of the cost of some of the other common diiunctional phenols, such as butyl, amyl, octyl and nonyl phenols. A mixture of phenols giving a product of substantially the same effectiveness as that obtained from the more expensive phenol affords a definite economic advantage. Further, sometimes mixtures of phenols give products which appear to be more effective than products obtained from a single phenol. Thus, products obtained from mixtures of butyl or amyl phenol, methyl phenol, nonyl phenol, decyl phenol and other phenols in some instances appear to have a greater effectiveness than products obtained from single phenols, even towards water.

CROSS REFERENCE angst? though there is not any savingin cost in the "production of products from such mixtures.

Because of low cost, mixturesin which cresol is one of the phenolic reactants are of particular importance. We have usedmixtures employing a cresol and another phenol in molar ratios ranging from 1:9 to 9:1, and found them-effective. Difunctional Xylenols, although they give eifective agents in mixtures'of this kind, are usually more expensive and do notoffer this economic advantage. Mixtures in which salicylic acid is one of the phenolic" reactants'or in which other phenols having a; substituentwith a reactive or labile hydrogen atom are used, are also of importance because the reactive group, such as the carboXyl group of salicylic acid, a ifords an opportunity for a numberof variationssuch as reaction with amines, alcohols, and the like, to

produce products of modified character which are useful in practicingthe' invention.

Although any conventional procedure ordinarily employed may be used in the manufacture of the herein contemplated resins or, for that matter, such resins may be purchased in the open market, we have foundit particularly desirable to use the procedures described elsewhere herein, and employing a combination of an organic sulfo-acid and a mineral acid as a catalyst, and Xylene as a solvent. By way of illustration, certain subsequent examples are included, butit isv to be understoodthe herein described invention-is not concerned'with the resins'per se or with any particular method of manufacture but is concerned with the use of derivatives obtained by the subsequent oxyalkylation thereof. The phenolaldehyde resins may be prepared in any suitable manner.

Oxyalkylation, particularly oxyethylation which is the preferred reaction, depends on contact between a non-gaseous phase and a. gaseous phase. It can, for example, be carriedout by melting the thermoplastic resin and subjecting it to treatment with ethylene oxide or the like, or by treating a suitable solution or suspension.

Since the melting points of the resins are often higher than desired inthe initial stage of oxyethylation, we have found it advantageousto use a solution or suspension of thermoplastic resin in an inert solvent such as xylene. Under such circumstances, the resin obtained in. the usual manner is dissolved by heating inxylene under a reflux condenser 01'' in. any other suitable manner. Since xylene or an equivalent inert solvent is present or may be present during oxyalkylation, it is obvious there is .no objection to having a solvent present during the resinifying stage if, in addition to beingiinert towards the resin,'it is also inert towards the reactants and also inert Numerous solvents, particularly of aromatic or cyclic nature, are suitably adapted for such use. Examples of such solvents are xylene, cymene, ethyl benzene, 'propyl benzene, mesitylene, decalin (decahydronaphthalene), tetralin (tetrahydronaphthalene) ethylene glycol diethylether, diethylene glycol diethylether, and tetraethylene glycol dimethylethenor mixtures of one or more. Solvents such as dichloroethylether, or dichloropropylether may be employed either alone or in mixture but have the objection that the chlorine atom in the compound may slowly combine with .the alkaline catalyst employed in oxyethylation. Suitable solvents may be selected from this group for molecular weight determinations.

The use of such solvents is a convenient exliquid reaction mass andthus preventsoverheating, and also because the solvent'can beemployed in connection with a reflux condenser and a water trap to assist in the removalof water'of reaction and also water present as partofthe formaldehyde reactant when anaqueous-solution offormaldehyde is used. Such aqueous solution, of course,-with the ordinary product 'of commerce containing about 37 /2'% to 40% formaldehyde, is the preferred reactant. When such solvent is used itis advantageously added at thebeginning of the resinification"procedure or before thereaction has proceeded very far;

Thesolvent can be removed afterwards by distillation with or withoutthe use'ofvacuum; and a final higher temperature canl'oe employed to complete reaction'if desired. Immany instances it is most-desirable to'pcrmit part of'the solvent, particularly when it is inexpensive, e. g;, xylene, to remain behind-in a predetermined amountso as to have a resin which can be handled more conveniently in the oxyalkylation stage. if a more expensivesolvent; such as decalin, is. em-

ployed, xylene orother 'inexpensive.solvent may tion, prior to oxyalkylation,falthough; if desired,

this reactive position may be oxyalkylated along with the phenolic hydroxyls. Thus; resins derived from-such phenols as "salicylic acid. can be reactedwithreagents such as alcohols, ethylene glycol, glycerol, triethanolamine, other amines, and the like, prior to oxyalkylation; Resins prepared from phenols havingester linked substituents, such as methyl salicylate may; prior to oxyalkylation, be subjectedto alcoholysis or reesterification to replacea portion of the ester linked radical with anothergroupwhich imparts to the final product improved characteristics. Thus, methyl salicylate isthe least expensive 'salicylate. It is readily converted toaldehyde linked resins, which onoxyalkylationgive usefulproducts; but products in which the methyl group of such a resin is replacedby alcoholysis by ahigher radical, such as results from alcoholysis with hexyl alcohol, amyl alcohol, butyl alcohol, benzyl alcohol, decyl alcohol, cyclohexyl alcohol, oleylalcohol, styryl alcohol, and thelike, on oxyalkylation give still more effective demulsifying agents. As a matter of fact the mostvaluable materials prepared with the use of salicylic acid asaresinogen are materials in which the salicylic acid is used in admixture with other phenols asyfor example, in resins produced fromabout four molar, proportions of para-amyl-phenol and" one molar proportion or" salicylic acid.

In preparing resins "from difunctional phenols it is common to employ reactants of technical grade. The substituted" phenols hereirrcontemplated are usually derived 'fromhydroxy-benzene. As a rule, such substitutedphenols are comparatively free from unsubstituted phenol. We have generally found that the amount present is considerably less than 1% and not infrequently in the neighborhood of of 1%, or even less. The amount of the usual trifunctional phenol, such as hydroxybenzene or metacresol, which canbe tolerated" is determined by the factthat actual cross-linking, if it' takes place-even infrequently,

SEARCH ROOM must not be sufiicient to cause insolubility at the completion of the resinification stage or the lack of hydrophile properties at the completion of the oxyalkylation stage.

The exclusion of such trifunctional phenols as hydroxybenzene or metacresol is not based on the fact that the mere random or occasional inclusion of an unsubstituted phenyl nucleus in the resin molecule or in one of several molecules, for example, markedly alters the characteristics of the oxyalkylated derivative. The presence of a phenyl radical having a reactive hydrogen atom available or having a hydroxymethyl or a substituted hydroxymethyl group present is a potential source of cross-linking either during resinification or oxyalkylation. Cross-linking leads either to insoluble resins or to non-hydrophilic products resulting from the oxyalkylation procedure. With this rationale understood, it is obvious that trifunctional phenols are tolerable only in a minor proportion and should not be present to the extent that insolubility is produced in the resins, or that the product resulting from oxyalkylation is gelatinous, rubbery, or at least not hydrophile. As to the rationale of resinification, note particularly what is said hereafter in differentiating between resoles, Novolaks, and resins obtained solely from difunctional phenols. The increased tolerance of phenols with relatively large substituent groups toward the presence of trifunctional phenols has already been pointed out.

Previous reference has been made to the fact that fusible organic solvent-soluble resins are usually linear but may be cyclic. Such more complicated structure may be formed, particularly if a resin prepared in the usual manner is converted into a higher stage resin by heat treatment in vacuum as previously mentioned. This again is a reason for avoiding any opportunity for cross-linking due to the presence of any appreciable amount of trifunctional phenol. In other words, the presence of such reactant may cause cross-linking in a conventional resinification procedure. or in the oxyalkylation procedure,

or in the heat and vacuum treatment if it is employed as part of resin manufacture.

Our routine procedure in examining a phenol for suitability for preparing products to be used in practicing the invention is to prepare a resin employing formaldehyde in excess (1.2 moles of formaldehyde per mole of phenol) and using an acid catalyst in the manner described hereinafter in Example la. If the resin so obtained is solvent-soluble in any one of the aromatic or other solvents previously referred to, it is then subjected to oxyethylation. During oxyethylation a temperature is employed of approximately 150 to 165 C. with addition of at least 2 and advantageously up to 5 moles of ethylene oxide per phenolic hydroxyl. The oxyethylation is advantageously conducted so as to require from a few minutes up to 5 to hours. If the product so obtained is solvent-soluble and self-dispersing or emulsifiable, or has emulsifying properties, the phenol is perfectly satisfactory from the standpoint of trifunctional phenol content. The solvent may be removed prior to the dispersibility or emulsifiability test. When a product becomes rubbery during oxyalkylation due to the presence of a small amount of trireactive phenol, as previously mentioned, or for some other reason, it may become extremely insoluble, and no longer qualifies as being hydrophile as herein specified. Increasing the size of the aldehydic nucleus, for

i6 instance using heptaldehyde instead of formaldehyde, increases tolerance for trifunctional phenol.

The presence of a trifunctional 0r tetrafunctional phenol (such as resorcinol or bisphenol A) is apt to produce detectable cross-linking and insolubilization but will not necessarily do so, especially if the proportion is small. Resinification involving difunctional phenols only may also produce insolubilization, although this seems to be an anomaly or a contradiction of what is sometimes said in regard to resinification reactions involving difunctional phenols only. This is presumably due to cross-linking. This. appears to be contradictory to what one might expect in light of the theory of functionality in resinification. It is true that under ordinary circumstances, or rather under the circumstances of conventional resin manufacture, the procedures employing diiunctional phenols are very apt to, and almost invariably do, yield solvent-soluble, fusible resins. However, when conventional procedures are employed in connection with resins for varnish manufacture or the like, there is involved the matter of color, solubility in oil, etc. When resins of the same type are manufactured for the herein contemplated purpose, 1. e., as a raw material to be subjected to oxyalkylation, such criteria of selection are no longer pertinent. Stated another Way, one may use more drastic conditions of resinification than those ordinarily employed to produce resins for the present purposes. Such more drastic conditions of resinification may include increased amounts of catalyst, higher temperatures, longer time of reaction, subsequent reaction involving heat alone or in combination with vacuum, etc. Therefore, one is not only concerned with the resinification reactions which yield the bulk of ordinary resins from difunctional phenols but also and particularly with the minor reactions of ordinary resin manufacture which are of importance in the present invention for the reason that they occur under more drastic conditions of resinification which may be employed advantageously at times, and they may lead to cross-linking.

In this connection it may be well to point out that part of these reactions are now understood or explainable to a greater or lesser degree in light of a most recent investigation. Reference is made to the researches of Zinke and his coworkers, Hultzsch and his associates, and to Von Eulen and his co-workers, and others. As to a bibliography of such investigations, see Carswell, Phenoplasts, chapter 2. These investigators limited much of their work to reactions involving phenols having two or less reactive hydrogen atoms. Much of what appears in these most recent and most up-to-date investigations is pertinent to the present invention insofar that much of it is referring to resinification involving difunctional phenols.

For the moment, it may be simpler to consider a most typical type of fusible resin and forget for the time that such resin, at least under certain circumstances, is susceptible to further complications. Subsequently in the text it will be pointed out that cross-linking or reaction with excess formaldehyde may take place even with one of such most typical type resins. This point is made for the reason that insolubles must be avoided in order to obtain the products herein contemplated for use as demulsifying agents.

The typical type of fusible resin obtained from a para-blocked or ortho-blocked phenol is clearly differentiated from the Novolak type or CROSS REFERENCE resole type of resin. Unlike the resole type, such typical type para-blocked or ortho-blocked phenol resin may be heated indefinitely without passing into an infusible stage, and in this respect is similar to a Novolak. Unlike the Novolak type the addition of a further reactant, for instance, more aldehyde, does not ordinarily alter fusibility of the difunctional phenol-aldehyde type resin; but such addition to a Novolak causes cross-linking by virtue of the available third functional position.

What has been said immediately preceding is subject to modification in this respect: It is well known, for example, that difunctional phenols, for instance, paratertiaryamylphenol, and an aldehyde, particularly formaldehyde, may yield heat-hardenable resins, at least under certain conditions, as for example the use of two moles of formaldehyde to one of phenol, along with an alkaline catalyst. This peculiar hardening or curing or cross-linking of resins obtained from difunotional phenols has been recognized by various authorities.

The compounds herein used must be hydrophile or sub-surface-active or surface-active as hereinafter described, and this precludes the formation of insolubles during resin manufacture or the subsequent stage of resin manufacture where heat alone, or heat and vacuum, are employed, or in the oxyalkylation procedure. In its simplest presentation the rationale of resinification involving formaldehyde, for example, and a difunctional phenol would not be expected to form cross-links. However, cross-linking sometimes occurs and it may reach the objectionable stage. However, provided that the preparation of resins simply takes into cognizance the present knowledge of the subject, and employing preliminary, exploratory routine examinations as herein indicated, there is not the slightest difficulty in preparing a very large number of resins of various types and from various reactants, and by means of different catalysts by different procedures, all of which are eminently suitable for the herein described purpose.

Now returning to the thought that cross-linking can take place, even when difunctional phenols are used exclusively, attention is directed to the following: somewhere during the course of resin manufacture there may be a potential crosslinking combination formed but actual crosslinking may not take place until the subsequent stage is reached, i. e., heat and vacuum stage, or oxyalkylation stage. This situation may be related or explained in mrms of a theory of flaws, or Lockerstellen, which is employed in explaining flaw-forming groups due to the fact that a CIIZOH radical and H atom may not lie in the same plane in the manufacture of ordinary phenol-aldehyde resins.

Secondly, the formation or absence of formation of insolubles may be related to the aldehyde used and the ratio of aldehyde, particularly formaldehyde, insofar that a slight variation may, under circumstances not understandable, produce insolubilization. The formation of the insoluble resin is apparently very sensitive to the quantity of formaldehyde employed and a slight increase in the proportion of formaldehyde may lead to the formation of insoluble gel lumps. The cause of insoluble resin formation is not clear, and nothing is known as to the structure of these resins.

All that has been said previously herein as re gards resinification has avoided the specific ref-..

18 erence to activity of a methylene hydrogen atom; Actually there is a possibility that under some drastic conditions cross-linking may take place through formaldehyde addition to the methylene bridge, or som other reaction involving a methylene hydrogen atom.

Finally, there is some evidence that, although the meta positions are not ordinarily reactive, possibly at times methylol groups or the like are formed at the meta positions; and if this were the case it may be a suitable explanation of abnormal cross-linking.

Reactivity of a resin towards excess aldehyde, for instance formaldehyde, is not to be taken as a criterion of rejection for use as a reactant. In other words, a phenol-aldehyde resin which is thermoplastic and solvent-soluble, particularly if xylene-soluble, is perfectly satisfactory even though retreatment with more aldehyde may change its characteristics markedly in regard to both fusibility and solubility. Stated another way, as far as resins obtained from difunctional phenols are concerned, they may be either formaldehyde-resistant or not formaldehyde-resistant.

Referring again to the resins herein contemplated as reactants, it is to be noted that they are thermoplastic phenol-aldehyde resins derived from difunctional phenols and are clearly distinguished from Novolaks or resoles. When these resins are produced from difunctional phenols and some of the higher aliphatic aldehydes, such as acetaldehyde, the resultant is often a comparatively soft or pitchlike resin at ordinary temperature. Such resins become comparatively fluid at to C. as a rule and thus can be readily oxyalkylated, preferably oxyethylated, without the use of a solvent.

Reference has been made to the use of the word fusible. Ordinarily a thermoplastic resin is identified as one which can be heated repeatedly and still not lose its thermoplasticity. It is recognized, however, that one may have a resin which is initially thermoplastic but on repeated heating may become insoluble in an organic solvent, or at least no longer thermoplastic, due to the fact that certain changes take place very slowly. As far as the present invention is concerned, it is obvious that a resin to be suitable need only be sufficiently fusible to permit processing to produce our oxyalkylated products and not yield insolubles or cause insolubilization or gel formation, or rubberiness, as previously described. Thus resins which are, strictly speaking, fusible but not necessarily thermoplastic in the most rigid sense that such terminology would be app-lied to the mechanical properties of a resin, are useful intermediates. Th bulk of all fusible resins of the kind herein described are thermoplastic.

The fusible or thermoplastic resins, or solvent-soluble resins, herein employed as reactants, are water-insoluble. or have no appreciable hydrophile properties. The hydrophile property is introduced by oxyalkylation. In the hereto appended claims and elsewhere the expression water-insoluble is used to point out this char acteristic of the resins used.

In the manufacture of compounds herein employed, particularly for demulsification, it is obvious that the resins can be obtained by one of a number of procedures. In the first place, suitable resins are marketed by a number of companies and can be purchased in the open market; in the second place, there are a wealth of exam- SEARCH R00 19 ples of suitable resins-described in th literature. The third procedure is to follow the directions or the present application.

The following examples, to to 20a, give specific directions for preparing oxyal-kylation-susceptible, water-insoluble, organic solvent-soluble, fusible, phenolic resins which may be used :to prepare the products used in the practice of the invention. Additionally, w directattention to Examples la to ZQSaof our application Serial No. 8,722, filed'on the'same day this application was filed, as illustrating suitable resins for this purpose. Examples lb to Hlb illustrate carrying out the -oxyalkylation procedure to produce products useful in the practice of the invention. Again we direct'attention to Examples lb to 1612 and Zeb to b of our application Serial No. 8,722 as illustrating products useful for the practice of this invention. Examples lc to illustrate theuse of the products for demulsification.

Example 111 Grams Para-tertiary butylphenol (1.0 mole) 150 Formaldehyde 37% (1.1 mole) 81 Concentrated HCl 1.5

Monoalkyl (Cw-C20, principally 012-014) benzene monosulfonic acid sodium salt 0.8 Xylene 100 (Examples of alkylaryl sulfonic acids which serves as catalysts and as emulsifiers particularly in the formof sodium salts include the following:

SOLsH tR is an alkyl'hydrocarbonradical having '12-'14 carbon a. oms.

B is an .alkyl radical having 3-12 carbonatoms and n represents the numeral 3, 2, or 1, usually 2. in such instances where R contains less than 8 carbon atoms.

With respect to alkylaryl sulfonic acids or the sodium salts, we have employed a monoalkylated benzene monosulfonic acid or the sodium salt thereof wherein the alkyl group contains 10 to 14 carbon atoms. We have found equallyeffective and interchangeable the following specific sulfonic acids or their sodium salts: A mixture of diand tripropylated' naphthalene monosulfonic acid; diamylated'naphthalene monosulfonic acid; andnonylnaphthalene monosulfonic acid.)

The equipment used was'a conventional'twopiece laboratory resin pot. The cover part of the equipment had. four openings: One for reflux condenser; one for the stirring device; one for a separatory funnel or other means of adding reactants; and a thermometer well. In. the manipulation employed, theseparatory funnel 'in-' sert for adding reactants wasnot used. The device was equipped with a combination refiuxand water-trap apparatus so that the single piece of apparatus could be used as either a reflux condenser'o-ra water trap,dependingon the position of the three-way glass stopcock. This permitted convenient-withdrawal of water from the water trap. "The equipment, furthermore, permitted any setting of the'valve'without disconnecting the equipment. The resin pot washeated with a glass :fiber electrical .heatenconstructed 2&- It waswsemiesoft or pliable :inwconsi'stency. w Sea extensively cross-linked resinmolecules.

, catalyst to fit snuglyaroundlthe resin pot. 'Such'heaters, with regulators, are readily available.

The phenol, formaldehyde, acid catalyst, and solvent were combined in the resin pot above'described. This particularphenol was in the form of a flaked solid. .Heat wasapplied with gentle stirring and the temperature was raised to -85 0., at which point a mild exothermic reaction took place. This reaction raised the temperature to approximately IDS- C. The reaction mix ture was then permitted to reflux at 100-105" C. for between one and one and one-half hours. The reflux trap arrangement was then changed from the reflux position to the normal water'entrapment position. The water of solution and the water of reaction were permitted to distill out and collect in the trap. As the water distilled out, the temperature gradually increased to approximately "C. which required between 1.5 to 2 hours. At this point the water recovered in the trap, after making allowance for a small amount of water held up in the solvent, corresponded to the expected quantity.

The solvent solution so obtained was used as such in subsequent oxyalkylation steps. We have also removed the solvent by conventional means, such as evaporation, distillation or vacuum distillat'on, and we customarily take a small sample of the solvent solution and evaporate the solvent to note the characteristics "of the solvent-free resin. The resin obtained in the operation above described was clear, light amber colored, hard, brittle. and had a melting point of -165 C.

Attention is directed to the fact that tertiary butylphenol, in presence of astrong mineral acid as a catalyst and using formaldehyde, sometimes yields a resin which apparentlyhas a very'slight amount of cross-elinking. Such resin is similar to the one described aboveexcept that it is somewhat opaque, and its melting po'ntis higher than the one described above-and there is a tendency to cure. Such a resin is generally dispersible in xylene but not solubleto give a clear solution. Such dispersion can-be oxyalkylated in thesame manner as the clear resin. If-desired, a minor proportion of another and inert solvent, such as diethyleneglycol diethylether, may be employed along with xylene, to give a clear solution prior to oxyalkylation. This fact of solubilization shows the present resin molecules are still quite small, as contrasted with the very large size of If following a given procedure with a given lot of the phenol, such a resin is obtained, the amount of employed is advantageously reduced slightly or the time ofreflux reduced slightly, or both, or an acid such as oxalic acid is used instead of hydrochloric acid. Purely as a matter of convenience-due to better solubility in xylene,

we prefer to use a clear resin but if desired either type may be employed.

Example 2a The same procedure was followed as in Exwas replaced by an equal amount of para-secondary butylphenol. The phenol was a solid of a somewhat mushy appearance, resembling moist cornmeal rather'than dry flakes. The appearance of the resin was substantially identica1 with that describedin Example la, preceding. The solvent-free resin was reddish-amber in color, somewhat opaque but completely.xylene-soluble.

CRUSS REFERENCE what is said in Example 1a, preceding, in regard to the opaque appearance of the resin. What is said there applies with equal force and efiect in the instant example.

Example 3a Grams Para-tertiary amylphenol (1.0 mole) 164 Formaldehyde 37% (1.0 mole) 81 E01 (concentrated) 1.5

Monoalkyl (Cm-C20, principally C12-C14) benzene monosulfonic acid sodium salt. 0.8 Xylene 100 The procedure followed was the same as that used in Example 1a, preceding. The phenol employed was a flaked solid. The solvent-free resin was dark red in color, hard, brittle, with a melting point of l28-140 C. It was xylene-soluble.

Example 4a The same procedure was employed as in Example la, preceding, using 198 grams of commercial styrylphenol and 150 grams of xylene. Styrylphenol is a white solid. The resin was reddish black in color, hard and brittle, with a melting point of about 80 to 85 C.

Example 5a Grams Para-tertiary amylphenol (1.0 mole) 164 Formaldehyde 37% (0.8 mole) 64.8 Glyoxal 30% (0.1 mole) 20.0 Concentrated HCl 2 Monoalkyl (Cm-C20, principally 012-014) benzene monosulfonic acid sodium salt .75

Xylene 150 This resin was prepared using the same equipment, and the same procedure as in Example 1a, preceding. The resin contained a slight amount of insoluble material which was removed by flltration of the xylene solution. This slight amount of insoluble material may have been the result of some very minor decomposition, due to the fact that the glyoxal was an aged sample. After removal of the small amount of insoluble material, the xylene was removed by distillation. The resultant resin was reddish amber in color, soft or liquid in consistency and xylene-soluble.

Example 6a Grams Para-tertiary butylphenol (1.0 mole) 150 Acetaldehyde 44 Concentrated H2SO4 2 Xylene 100 The phenol, acid catalyst, and 50 grams of the xylene were combined in the resin pot previously described under Example 1a. The initial mixture did not include the aldehyde. The mixtur was heated with stirring to approximately 150 C. and permitted to reflux.

The remainder of the xylene, 50 grams, was then mixed with the acetaldehyde; and this mix ture was added slowly to the materials in the resin pot, with constant stirring, by means of the separatory funnel arrangement previously mentioned in the description of the resin pot in Example la. Approximately 30 minutes were required to add this amount of diluted aldehyde. A mild exothermic reaction was noted at the first addition of the aldehyde. The temperature slowly dropped, as water of reaction formed, to about 100 to 110 C., with the reflux temperature being determined by the boiling point of water; After all the aldehyde had been added, the reactants were permitted to reflux for between an hour to an hour and a half before removing the water by means of the trap arrangement. After the water was removed the remainder of the procedure was essentially the same as in Example 1a. When a sample of the resin was freed from the solvent, it was dark red, semi-hard or pliable in consistency, and xylene-soluble.

Example 7a Grams Para-tertiary amylphenol 164 Furfural 96 Potassium carbonate 8 The furiural was shaken with dry sodium carbonate prior to use, to eliminate any acids, etc. The procedure employed was substantially that described in detail in Technical Bulletin No. 109 of the Quaker Oats Company, Chicago, Illinois. The above reactants were heated under the reflux condenser for two hours in the same resin pot arrangement described in Example 1a. The separatory funnel device was not employed. No xylene or other solvent was added. The amount of material vaporized and condensed was comparatively small except for the water of reaction. At the end of this heating or reflux period, the trap was set to remove the water. The maximum temperature during and after removal of water was approximately 202 C. The material in the trap re resented 16 cc. water and 1.5 cc. furfural. The resin was a bright black, hard resin, xvlenesoluble. and had a meltin point of to C.. with some tendency towards being slowly curable. We have also successfully followed this same procedure using 3.2 grams of potassium carbonate instead of 8.0 grams.

Example 8a Grams Para-tertiary amylphenol 492 Formaldehyde, 3 528 NaOH in 30 cc. H2O 6.8

Monoalkyl (Cm-Cm, principally 012-014) benzene monosulfonic acid sodium salt 2.0

Xylene 200 The above reactants were combined in a resin pot similar to that previously described, equipped with stirrer and reflux condenser. The reactants were heated with stirring under reflux for 2 hours at 100 to 110 C. The resinous mixture was then permitted to cool sufficiently to permit the addition of 15 ml. of glacial acetic acid in 150 cc. H2O. On standing, a separation was effected, and the aqueous lower layer drawn off. The upper resinous solution was then washed with 300 ml. of water to remove any excess HCHO, sodium acetate, or acetic acid. The xylene was then removed from the resinous solution by distilling under vacuum to 150 C. The resulting resin was clear, light amber in color, and semifluid or tacky in consistency.

Example 9a Resin of Example 8a was subjected to vacuum distillation to 225 C., at 25 mm. Hg. The resulting product was a hard, brittle resin, xylenesoluble, and having a melting point of -150 C.

Example 10a Grams Commercial para-tertiary amylphenol 328 Formaldehyde (37%) 352 NaOH in 20 cc. H2O 4.5

Monoalkyl (Cm-C20, principally 012-014) benzene monosulfoniaacidsodium salt 1.5

SEARCH R0001 :The: above; reactantswere: refluxed with :stirring for.2;hours. 1.200 gramsof xylene were then added and the whole cooled .to 90-100 C., and the NaOEneutralized with 10 cc. glacial acetic acid in 100cc. H2O. The mass was allowed to stand, effectinga separation. The lower aqueous layer waswithdrawn and the upper resinous solution was washed with water. After drawing off the wash water, the xylene solution was subjected to vacuum distillation, heating to 150 C. The resulting solvent-free resin .was xylene-soluble, soft or tacky in consistency," and pale yellow or light amber in color.

On heating further, without vacuum distillation, the following physical changes were noted:

The above distillation was without the use of vacuum. ,It illustrates that heating alone, or heating 'with vacuum, changes a low-stage resin into a medium .or high-stage resin.

Example 11a Grams Menthylphenol (3.0..moles) 696 Heptaldehyde (3.0 moles) 34:3 Concentrated H2504 6 Xylene 500 The procedure employed was essentially the same as in Example 611 where acetaldehyde was employed, but with the difference that due to the factthat heptaldehyde is' a higher boiling aldehyde, it was not necessary to dilute it with thexylene. For this reason all the xylene was added to ,the initial mixture, and the heptaldehyde .was added by means of the separatory funnel arrangement. Thus,'the phenol, acid catalyst, and solvent were combined in a resin pot by the same procedure usedin Example 6a. The

resin, after removal of the solvent by distillation, was clear, dark red in color, had; a soft, tacky appearance and was xylene soluble.

Example 12a Grams Nonylphenol (31 moles) 6820 Formaldehyde 37% (42 moles) 34-30 NaOH (in 200 0.0; H20) 93 Xylene 2040 The above reactants'were combined in a -gallon autoclave and .heated with stirring in the following manner:

Pounds per "Time Temperature Square Inch :30 a; In 25 0 11:00 a. m 100 11:30 a. m 127 40 1 :00 N 148 60 15 0 177 130 11.0 185 160 2: .194 185 The; reaction-was stopped-.atzthisgpoint, sumcientcooling water was applied to lowerxthe temperature to approximately 0., or cool 'enough to permit opening the autoclave and adding 202 grams of glacial acetic acid to neutralize the NaOH.

The product was then removed from the autoclave and the resin, solution diluted further so as to effect a ready separation of the aqueous layer. After twice washing with water to remove the excess formaldehyde, acetic acid and formed salt, the resin was subjected to vacuum distillation to 149 C. at'25 mm. Hg vacuum. The resulting resin was reddish black in color, xylene-soluble, hard but not brittle, and had a melting point of to 0.

Example 13a Grams Butyl salicylate (2.0 moles) 388 Formaldehyde 37% (2.3 moles) 182 Concentrated HCl 20 Monoalkyl (Cm-C20, principally 012-014) benzene monosulfonic acid sodium salt 25 Xylene 200 The same procedure was followedas .in Example 1a. The resin was soft, and amber in color.

Example 14a Grams Amyl salicylate (2.0moles) 416 Formaldehyde 37% (2.3 moles) 182 Concentrated I-ICl 20 lvionoalkyl (Cm-C20, principally C12-C14) benzene monosulfonic acid sodium salt 25 Xylene 200 The same procedure was followed in Example 1a. The resin was soft and amber in color.

Example 15a Grams Octyl salicylate (2.0 moles) 500 Formaldehyde 37% (2.3. moles) 1,82 Concentrated HCl 25 Monoalkyl (Clo-C20, principally C12-C14) benzenemonosulfonic acid sodium salt 3.0 Xylene 250v The same procedure was followed as in Example 1a. The resin was soft, and amber in color.

Erample 16a Grams Para-hydroxy ethylbenzoate 156 Formalin (formaldehyde 37%) .88 Oxalic acid (dissolved in 1 part water) 1.6

Examplefla Grams Salicylic acid (2.0 moles) 276 HCHO 37%v (2.0 moles) u- .162 Water .600 Xylene," l

The same .procedure was followed as in Example 1a preceding. except. that the reflux period was 8 hours. .At the end of'this time there. was

EROSS REFER lib? still a strong odor of formaldehyde present in the vapors and there was present in the flask unreacted salicylic acid. For this reason another mole of formaldehyde was added (81 more grams) and the resinification period repeated for another 8 hours. At the end of this time the water was distilled oii along with the unreacted formaldehyde.

The value of salicylic acid as a resin-making compound for the production of compounds for use in the present invention rests not so much in the use of the product as such, as in its use in admixture with other phenolic reactants. Thus, if one makes a mixture of approximately 4 moles of para-amylphenol, for example, and one mole of salicylic acid and resinifies the mixture, there are two advantages; (1) the mixture is soluble, or at least it can be handled in xylene much more advantageously than resins from salicylic acid alone, and (2) one obtains a resin which has certain possibilities for further reaction which are not present in the usual hydrocarbon substituted phenol resin. A resin molecule is obtained which may be indicated in its simplest aspect in the following manner.

The above formula is, of course, an idealized structure for obvious reasons because the salicylic acid nucleus presumably can appear at any point in the resin molecule. Such resin, or for that matter a resin having an increased number of salicylic acid radicals, can be oxyalkylated in the same manner as other phenol-aldehyde resins.

The reactive carboxyl radical permits a number of variations. Thus, the resin can be reacted with reagents such as ethylene glycol, glycerol, triethanolamine, diethanolamine, etc.

Example 18a Grams Salicylic acid (0.5 mole) 69 Para-tertiaryamylphenol (2.0 moles) 328 Monoalkyl (Clo-C20, principally C12-C14) benzene monosulphonic acid sodium salt 1.5 Concentrated HCl 20 Xylene 400 Formaldehyde 37% 208 The same procedure was followed as in Example la, except that the amount of hydrochloric acid employed is comparatively high, to wit, 20 grams, and the reflux time, instead of being 1 hours is 3 hours. Only a very small amount of salicylic acid was lost on evaporation. The resin is soft and tacky, and xylene-soluble.

Example 19a The same procedure was followed as in the preceding example, through the point where all the water had been removed, leaving the anhydrous resin in the solution of xylene. The temperature at this point was about 145 C. Eighty-five grams of triethanolamine, commercial grade (about mole) were then added. More xylene was then allowed to distill out until the temperature rose to 180 to 185 C. The mass was then allowed to reflux at this temperature for approximately three hours with the usual trap arrangement. During this period substantially all the water of esterification was eliminated, the amount of water being approximately cubic centimeters.

When all the water had been eliminated the xylene which distilled out earlier between the range of to 185 0., was again added to the mixture so as to give a uniform solution containing about 60 parts of resin and 40 parts of xylene.

The cheapest salicylate is methylsalicylate. A resin can be prepared from methylsalicylate alone or methylsalicylate in combination with paraamylphenol, para-butylphenol, or any one of a number of other phenols as described, and then the resin can be subjected to alcoholysis in presence of an alkali so as to replace the methyl radical by some higher alkyl radical. This is illustrated by alcoholysis with hexyl. alcohol, octyl alcohol, decyl alcohol, benzyl alcohol, cyclohexyl alcohol, olcyl alcohol, styryl alcohol, ethyeneglycol, diethylene glycol, phenoxyethanol, etc. The salicylic acid ester of the corresponding alcohol is also useful as an initial raw material, in-

stead of methyl salicylate.

The carboxy radical of salicylic acid remaining in a salicylic acid resin, such as those illustrated above may be reacted, not only with ethyleneglycol and triethanolamine as illustrated but with other conventional reactants such as ammonia, primary amines such as amylamine, secondary amines such as diamylamine, ethyl ethanolamine, diethanolamine, butyl ethanolamine, and propanolamines, hexanolamines, butanolamines, pentanolamines, and cyclohexylamines and a variety of other suitable compounds in which the final efiect is simply that of an acylation reaction.

Example 200,

Grams Para-chlorophenol (1.0 mole) 128.5 Formaldehyde 37% (1.33 mole) 109 Concentrated HCl 3 Monoalkyl (Cm-C20, principally C12-C14) benzene monosulfonic acid sodium salt-.. .2 Xylene The same procedure was followed as described in Example 1a. The resulting resin was dark in color and hard and brittle in consistency.

Other phenols of the kind previously mentioned include dimethylaminomethylphenol. This is a mixture of CHIN-(CH3):

and

UH2N(OH3)2 As in the case of salicylic acid the most desirable products are those in which dimethylaminomethylphenol contributes a portion of the phenolic reactants.

The preceding examples illustrate some of the intermediate reactions, such as reaction with triethanolamine, ethyleneglycol, etc., useful with resins in which the phenol is substituted by a group having a reactive hydrogen. We have also reacted such products with chlorohydrin and subsequently with a tertiary amine and obtained useful products. We have made a number of such mixed resins using a variety of diiunctional phenols other than para-tertiaryamylphenol; for instance, :we have employed para-secondaryamyL- SEARCH room phenol, para-tertiarybutylphenol, para-secondarybutylphenol, para-octylpheno-l, para-nonylphenol, etc. We have then subjected the resins to intermediate steps of the kind described'in Example 19a and then subjected the products of reaction to oxyalkylation, such as oxyethylation, and obtained compounds which are of outstanding efiectiveness for demulsification of petroleum emulsions.

Attention is directed to a statement which appeared earlier in the instant section to the effect that when a substituent in a difunctional phenol was other than a hydrocarbon radical it might resemble either a cresol or an amylphenol when examined from the standpoint of the ultimate oxyalisylated compound, particularly as a de-- mulsiiier. Thus, chlorophenols give compounds of effectiveness, as demulsifiers comparable to that of compounds derived from ortho or paracresol. On the other hand propylsalicylate, butylsalicylate, octylsalicylate, and the like yield compounds comparable in effectiveness to those de rived from butylphenol.

In a number of the foregoing examples, phenols have been identified without specific designation of the position of substitution or the'structure of the substituent radical. In suchcases, the phenols meant are either the commercial products distributed under these names, or, if the products are not commercially available, the products obtained by customary syntheses from phenol, meta-cresol or 3,5-xylenol, and consist mainly of the parasubstituted product, usually associated with some of the orthosubstituted product, perhaps a very small proportion of metasubstituted material, some impurities, etc. Also, .it is to be understood that all oi the products of the foregoing examples, unless it is otherwise'stated in the example, aresoluble in xylene, at least to an extent suhlcientto permit the use of xylene as the solvent in oxyalkylation.

As far as the manufacture or resins is concerned it is usually most convenient to employ a catalyst such as illustrated by previous examples.

It is extremely dimcult to depict the structure of a resin derived from a single phenol. When mixtures of phenols are used, even in equimolar proportions, the structure" of the resin is even more indeterminable. In other words, a mixture involving para-butylphenojl and para-amylphenol might have an alternation of the two nuclei or one might have a series of 'butylated nuclei and then a series of amylated nuclei. If a mixture of aldehydes is employed, for instance, acetalde hyde and butyraldehyde, .or acetaldehyde and formaldehyde, or benzaldehyde and acetaldehyde, the final structure ofthe resin becomes even more complicated and possibly depends on the relative reactivity of the aldehydes. For that matter, one might be producing simultaneously two diiierent resins, in what would actually be a mechanical mixture, although such mixture might exhibit some unique properties as compared with a mixture of the same'two resins prepared separately. Similarly, as has been suggested, one might use a combination of oxyalliylating agents; for instance, one might partially oxyalkylate with ethylene oxide and then finish off with propylene oxide. It is understood that the use of oxyalkylated derivatives of such resins, derivedirom such plurality of reactants instead of being limited to a single reactant from each of the three classes, .is contemplated and here inable .alkylene oxides in all cases.

28 'cludedfor the reason that theyare obvious-variants.

Having obtained a-suitable resin oi the kind described, such. resin is subjectedto treatment with a low molalreactive alpha-beta olefin oxide so as to render the product distinctly hydrophile in nature as indicated. by the fact that it becomes self-emulsifiable or miscible or soluble in water, or self-dispersible, or has emulsifying properties. If the phenolsubstituent has a reactive hydrogen atom, as in: salicylic acid resinstwo procedures are available, and both giveuseful products. In the first, the reactive position is blocked, as by esterification, or amidification, and the phenolic hydroxyls then oxyalkylated. In thesecond, the reactive position is oxyalkylated'along with the phenolic hydroxyls.

The olefin oxides employed for oxyalkylation arecharacterized. by the fact that the contain not over 4 carbon atoms and are selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycidaand methylglycide. Glycidem'ay be, of course, considered as a hydroxy, propylene oxideand'miethyl glycide as .a hydroxy butylene oxide. In anyevent, however, all such reactants contain the reactive ethylene oxide ring and may be best considered as derivatives of or substituted ethylene oxides. The solubilizing effect of the oxide is directly proportional to the percentage of oxygenpresent,0r specifically, to the oxygen-carbon ratio.

In ethylene oxide, the oxygen-carbon ratio is 112. In glycide, it is 2:3: and in methyl glycide, 1:2; In suclrcompounds'the ratio is very'favorable to the production of'hydrophile or surfaceactive porperties; However; theratio, in propylene oxide, is 1:3, and inbutylene oxide, 1:4. Obviously, such latter two reactants are satisfactorily employed only where the resin composition is such'as to make incorporation of the do? sired property practical. Inother. cases, they may produce marginally satisfactory derivatives, or even unsatisfactory derivatives. They are usable in conjunction withth'e three more favor- For instance, after one or several propylene oxideor but lene oxide molecules: haueibeen attached to the resin molecule,oxyalkylation may be satisfactorily continuedausing the i more favorable members of the class, to produce the desired hydrophile: product. Used alone, these two reagents may insome cases fails'to product ,sufiiciently hyd-rophile derivatives because of. their relatively low oxygen-carbon ratios.

Thus, ethylene oxideiismuch more efiective than propylene oxide, andpropylene oxide is more effective than butylene oxide. Hydroxy propylene oxide (a ly-bide) is more eiiective than propylene oxide. Similarly, hydroxybutylene oxide (methyl glycide) is more effective than butylene oxide. Since ethylene oxide is the cheapest alkylene oxide available and is reactive, its .use .is-definitely advantageous, and .espect-ially in light of its high oxygen content. Propylene oxide is less reactive than, ethylene oxide, and butylene oxide is definitelyless reactive than propylene oxide. On the other hand, g-lycide may react with almost explosive violence and must be handled with .extreme care- The oxyalkylation of resinsof thekind from which the products used in the practice of the present invention are prepared is advantageously catalyzed by the-presence of an alkali. Useful alkalinercata ysts include-soaps,- sodium acetate, sodium. hydroxide, sodium. methylate, caustic W038 REFERENCE potash, etc. The amount of alkaline catalyst usually is between 0.2 to 2%. The temperature employed ma vary from room temperature to as high as 200 C. The reaction may be conducted with or without pressure, i. e., from zero pressure to approximately 200 or even 300 pounds gauge pressure (pounds per square inch). In a general way, the method employed is substantially the same procedure as used for oxyalkylation of other organic materials having reactive phenolic groups.

It ma be necessary to allow for the acidit of a resin in determining the amount of alkaline catalyst to be added in oxyalkylation. For instance, if a nonvolatile strong acid such as sulfuric acid is used to catalyze the resinification reaction, presumably after being converted into a sulfonic acid, it may be necessary and is usually advantageous to add an amount of alkali equal stoichiometrically to such acidity, and include M final product used as a demulsifier, it is our preference to use xylene. This is particularly true in the manufacture of products from low-stage resins, i. e., of 3 and up to and including 7 units per molecule.

If a xylene solution is used in an autoclave as hereinafter indicated, the pressure readings of course represent total pressure, that is, the combined pressure due to xylene and also due to ethyleneoxide or whatever other oxyalkylating agent is used. Under such circumstances it may be necessary at times to use substantial pressures to obtain eflective results, for instance, pressures up to 300 pounds along with correspondingly high temperatures, if required.

However, even in the instance of high-melting resins, a solvent such as xylene can be eliminated in either one of two ways: After the introduction of approximately 2 or 3 moles of ethylene oxide, for example, per phenolic nucleus, there is a definite drop in the hardness and melting point of the resin. At this stage, if xylene or a similar solvent has been added, it can be eliminated by distillation (vacuum distillation if desired) and the subsequent intermediate, being comparatively soft and solvent-free, can be reacted further in the usual manner with ethylene oxide or some other suitablereactant.

Another procedure is to continue the reaction to completion with such solvent present and then eliminate the solvent by distillation in the customary manner.

Another suitable procedure is to use propylene oxide or butylene oxide as a solvent as well as a reactant in the earlier stages along with ethylene oxide, for instance, by dissolving the powdered resin in propylene oxide even though oxyalkylation is taking place to a greater or lesser degree. After a solution has been obtained which represents the original resin dissolved in propylene oxide or butylene oxide, or a mixture which includes the oxyalkylated product, ethylene oxide is added to react with the liquid mass until hydrophile properties are obtained. Since ethylene oxide is more reactive than propylene oxide or butylene oxide, the final product may contain 30 some unreacted propylene oxide or butylene oxide which can be eliminated by volatilization or distillation in any suitable manner.

Attention is directed to the fact that the resins herein described must be fusible or soluble in an organic solvent. Fusible resins invariably are soluble in one or more organic solvents such as those mentioned elsewhere herein. It is to be emphasized, however, that the organic solvent employed to indicate or assure that the resin meets this requirement need not be the one used in oxyalkylation. Indeed solvents which are susceptible to o-xyalkylation are included in this group of organic solvents. Examples of such solvents are alcohols and alcohol-ethers. However, where a resinis soluble in an organic solvent, there are usually available other organic solvents which are not susceptible to oxyalkylation, useful for the oxyalkylation step. In any event, the organic solvent-soluble resin can be finely powdered, for instance to 100 to 200 mesh, and a slurry or suspension prepared. in xylene or the like, and subjected to oxyalkylation. The fact that the resin is soluble in an organic solvent or the fact that it is fusible means that it consists of separate molecules. Phenol-aldehyde resins of the type herein specified possess reactive hydroxyl groups and are oxyalkylation susceptible.

Considerable of what is said immediately hereinafter is concerned with the ability to vary the hydrophile properties of the compounds used in the process from minimum hydrophile properties to maximum hydrophile properties. Even more remarkable, and equally difiicult to explain, are the versatility and utility of these compounds as one goes from minimum hydrophile property to ultimate maximum hydrophile property. For instance, minimum hydrophile property may be described roughly as the point where two ethyleneoxy radicals or moderately in excess thereof are introduced per phenolic hydroxyl. Such minimum hydro-phile property or sub-surfaceactivity or minimum surface-activity means that the product shows at least emulsifying properties or self-dispersion in cold or even in warm distilled water (15 to 40 C.) in concentrations of 0.5% to 5.0%. These materials are generally more soluble in cold water than Warm water, and may even be very insoluble in boiling Water. Moderately high temperatures aid in reducing the viscosity of the solute under examination. Sometimes if one continues to shake a hot solution, even though cloudy or containing an insoluble phase, one finds that solution takes place to give a homogeneous phase as the mixture cools. Such self-dispersion tests are conducted in the absence of an insoluble solvent.

When the hydrophile-hydrophobe balance is above the indicated minimum (2 moles of ethylene oxide per phenolic nucleus or the equivalent) but insuilicient to give a sol as described immediately preceding, then, and in that event hydrophile properties are indicated by the fact that one can produce an emulsion by having present 10% to 50% of an inert solvent such as xylene. All that one need to do is to have a xylene solution within the range of 50 to parts by weight of oxyalkylated derivatives and 50 to 10 parts by weight of xylene and mix such solution with one, two or three times its volume of distilled water and shake vigorously so as to obtain an emulsion which may be of the oil-in-water type or the water-in-oil type (usually the former) but, in any event, is due to the hydrophile-hydrophobe balance of the oxyalkylated derivative. We prebitHlibrl riuuln oncogene 3i fer simply to use the xylene diluted derivatives; which: are descri'bed elsewhere; for this test rather than evaporate the' sol'ventiand' employ any. more elaborate tests, if. the solubility isnot sufficientito permit the simplesol' test in water. previously noted.

If. the product is not readilywater solublev it may be dissolved in ethyl; or methyl alcohol, ethylene glycol diethylether; or diethylene glycol di'ethylether, with a little acetone added if required, making a rather concentratedsolution', for instance 443% to- 50%,v and. then adding enough of the concentrated; alcoholic or equivalent: solution. to give the previously suggested 0.5% to 5.0% strength solution. If the product' is self-dispersing (i. e., if the oxyallrylated product is a liquidor a liquid solution self.- -emulsifiable), such sol or dispersionis referred 'to as at least semi-stable in the sense that sols, emulsions, or dispersions prepared. are relatively. Sta/b163, if they remain at least for some period. of time, for instance 30 minutes to two'hours, before showing-any marked separation. Such tests are conducted at room temperature (22 0.). Needless to say, a test can be made in presence of an insolublesolven-t such as 5% to ofv xylene, as. noted in previous examples. If such mixture, i. e., containing a waterrinsoluble solvent, is at least semi-stable, obviously the solvent-free product would be even. more so. Surface-activity representing an advanced hydrophile- .hydrophobebalance canalso be determined by the use of conventional measurements hereinafter described. One outstandingcharacteristic prop-- erty, indicating surface-activity in a material is the ability to forma permanent foam in dilute :aqueous solution, for example, less than. 0.5%, when in the higher oxyalkylated stage, and. to form an emulsion in the lower and: intermediate .stages ofoxyalkylati'on.

Allowance must bemade for the presence ofsa. :solvent in the final product in relation to the. .hydrophile properties of the final product. The principle involved in the manufacture of the herein contemplated compounds for use as demulsifying agents, is based on the conversion of a hydrophobe; or non-hydrophil-e compound. or mixture'of. compounds into products which are: distinctly hydrophile, at least to the extent that; they have emulsifying properties or are selfemulsi-fying; that is, when shaken with. water they produce stable or semi-stable suspensions, or, the presence of a water-insolubie solvent, such a s-Xylene, an emulsion. In demulsification; it is sometimes preferable to use a producthaving markedly enhancedhydrophi-le properties over: and above the initial stage of selfemulsifiability;. although wehav'e found that with products cfthe type used herein, most eflicacious results are ob-- tained with products which do not h-ave-hydro:-- phile properties beyond the stage of self-dis-- persibility.

More highly oxyalkylated" resins give colloidal solutions or sols which show typical properties comparable to ordinary surface-activev agents;- Such conventional surface-activity may be measured by determining the surface tension' andthe interfacial tension against parafiin oil. or the like. At the initial and lower stages of oxyalkyla-- tion, surface-activity is not suitably determined in this same manner but one may. employ an: emulsification test. Emulsions come into existence as a rule through the presence-of a surface'- active emulsifying agent. someflsurfacaactive emulsifyingagents such asmahogany soap. may

32 produce awater-in-oil emulsion or an oil-ins water emulsion dependingupon the ratioof the two phases,d'egree of agitation, concentration of emulsifying agentgetc.

The same is true in regard to the oxyalkylated resins heremspecifiecl, particularly in the lower stage of oxyalkyl'ation', the so-called sub-surface-active" stage; The surfaceactive properties are readily demonstrated by producing a xylene-water emulsion. Asuitable procedurev is as follows: The oxyalkylated resin is dissolved in an equal 'weight of xylene; Such 50-50 solution: is then mixed with 1-3 volumes of water and shaken to produce an emulsion. The amount of'xyl'ene is. invariably suffi'cient to reduce even a tacky resinous product to a solution which is readily dispersi'ble' The emulsions so produced are usually-xylene in-water emulsions (oil-inwater type) particularly when the amount of distilled water used is at least slightly in excess of the volume of xylene solution and also if shaken vigorously. At times, particularly'in the lowest stage of oxyalkylation, one may obtain a waterin-xylene emulsion (water-in-oiltype) which is apt to r'e've'rse on more vigorousshaking and further dilution with water.

Ifin doubtas to this property, comparison with a resin obtained from para-tertiary butylphenol andformaldehyde (ratio 1 part phenol to 1.1 formaldehyde) using an acid catalyst and. then followed. by. oxyalkylationusing? moles of ethylene-oxide: for each phenolic hydroxyl, is helpful. Such resin. priortooxyalkylation has a molecular weight indicating about 4 /2 units per resin molecule. Such:v resim. when: diluted with an equal weight of' xylene, will serve to illustrate the above emulsification test.

In a few instances, the resin may-not be sufiicien-tly" soluble in xyleneal'one but may: require the addition of' some ethylene glycol diethylether as described .elsewhere. It is understood that such mixture, or any: other similar mixture, is considered. the equivalent of xylene for the purpose of this test.

Inmany cases, there is no doubt as to the presence or absence of hydrophile' or surface-active characteri'stics'in the products used in accordance with this invention; They dissolve or disperse in water; and such dispersions foam readily. With borderlinecases, i; e., those which show only incipient hydr'ophile or surface-active property (s'ub-surface-activity) tests for emulsifying properties or self-dispersibilit'y are useful. The fact that areagentis capable of producing a dis- .persion inwate'r is proof'that it isdistinctly hydrophile. doubtfulcases', comparison can be made with the butylphenol formaldehyde resin analog whereinz moles: of ethylene oxide have been introduced for each phenolic nucleus.

The; presence: of xylene or an' equivalent wa ter-insoluble solvent may mask the point at which a solvent-free product on more dilution in a test tube! exhibits 'self-emulsification; For

this: reason, if'it; is desirable to determine the approximate point where self-emulsification be-- girls, theiritis better to eliminate thexylene or equivalent: from asmall portion of the reaction mixture and test such portion. In some cases, such xylene-free resultant may show initial or incipient hydrophi'le properties, whereas in pres-- ence of. xylene such properties would not be noted... In other cases; thefirst' objective indication of 'hydrophileproperties may he the capac-- ity of the-material to emulsify an insoluble 501- ventsuch. as xylene; Itfis to bel emphasized that CROSS REFEREl-lllt.

hydrophile properties herein referred to are such as those exhibited by incipient self-emulsification or the presence of emulsifying properties and go through the range of homogeneous dispersibility or admixture with water even in presence of added water-insoluble solvent and minor proportions of common electrolytes as occur in oil field brines.

Elsewhere, it is pointed out that an emulsifica tion test may be used to determine ranges of surface-activity and that such emulsification tests employ a xylene solution. Stated another way,

it is really immaterial whether a xylene solution produces a sol or whether it merely produces an emulsion.

In light of what has been said previously in regard to the variation of range of hydrophile properties, and also in light of what has been said as to the variation in the effectiveness of various alkylene oxides, and most particularly of all ethylene oxide, to introduce hydrophile character, it becomes obvious that there is a wide variation in the amount of alkylene oxide employed, as long as it is at least 2 moles per phenolic nucleus, for producing products useful for the practice of this invention. Another variation is the molecular size of the resin chain resulting from reaction between the difunctional phenol and the aldehyde such as formaldehyde. It is well known that the size and nature or structure of the resin polymer obtained varies somewhat with the conditions of reaction, the proportions of reactants, the nature of the catalyst, etc.

Based on molecular weight determinations, most of the resins prepared as herein described, particularly in the absence of a secondary heating step, contain 3 to 6 or 7 phenolic nuclei with approximately 4 or /2 nuclei as an average. More drastic conditions of resinification yield resins of greater chain length. Such more intensive resinification is a conventional procedure and may be employed if desired. Molecular weight, of course, is measured by any suitable procedure, particularly by cyroscopic methods; but using the same reactants and using more drastic conditions of resinification one usually finds that higher molecular weights are indicated by higher melting points of the resins and a tendency to decreased solubility. See what has been said elsewhere herein in regard to a secondary step involving the heating of a resin with or without the use of vacuum.

We have previously pointed out that either an alkaline or acid catalyst is advantageously used in preparing the resin. A combination of catalysts is sometimes used in two stages; for instance, an alkaline catalyst is sometimes employed in a first stage, followed by neutralization and addition of a small amount of acid catalyst in a second stage. It is generally believed that even in the presence of an alkaline catalyst, thenumber of moles of aldehyde, such as formaldehyde, must be greater than the moles of phenol employed in order to introduce methylol groups in the intermediate stage. There is no indicaprepared by the use of an acid catalyst. possible that such groups may appear in the finished resins prepared solely with an alkaline catalyst; but we have never been able to confirm this fact in an examination of a large number of resins prepared by ourselves. however, is to use an acid-catalyzed resin, particularly employing. a formaldehyde-to-phenol.

ratio of 0.95 to 1.20 and, as far as we have been .65 tion that such groups appear in the final resinif It is Our preference,

. .34 able to determine, such resins are free from methylol groups. As a matter of fact, it is probable that in acid-catalyzed resinifications, the methylol structure may appear only momen- 5 tarily at the very beginning of thereaction and fashion. The conditions of reaction, as far as time or per cent are concerned, are within the range previously indicated. With suitable agitation the ethylene oxide, if added in molecular 8 to 24 hours. A useful temperature range is from 125 to 2259.0. The completion of the reaction of each addition of ethylene oxide in stepwise fashion is usually indicated by the reduction or elimination of pressure. An amount conveniently used for each addition is generally equivalent to a mole or two moles of ethylene oxide per hydroxyl radical. When the amount of ethylene oxide added is equivalent to approximately 50% byweight of theoriginal resin, 2. sample is tested forincipient hydrophile properties by simply shaking up in water as is, or after the elimination of the, solvent if a solvent is present. The amount of ethylene oxide used to obtain a useful demulsifying agent as a rule varies from 70% by weight of the original resin to as much as five or six times the weight of the original resin. In the case of a resin derived from para-tertiary butylphenol, as little as 50% by weight of ethylene oxide may give suitable solubility. With propylene oxide, even a greater molecular proportion is required and sometimes a resultant of only limited hydrophile properties is obtainable. .The same istrue to even a greater extent with butylene oxide. The hydroxylated alkylene oxides are more effective in solubilizing properties than the comparable compounds in which no hydroxyl is present.

Attention is directed to the fact that in the subsequent examples reference is made to the stepwise addition of. the alkylene oxide, such as ethylene oxide. It is understood, of course, there is no objection. to the continuous addition of alkylene oxide until the desired stage of reaction is reached. In fact, there may be less of a hazard involved and it is often advantageous to add the alkylene oxide slowly in a continuous stream and in such amount as to avoid exceeding the higher pressures noted in the various examples or elsewhere.

It may be well to emphasize the fact that when resins are produced from difunctional phenols and some of the higher aliphatic aldehydes, such as acetaldehyde, the resultant is a comparatively soft or pitch-like resin at ordinary temperatures. Such resins become comparatively fluid at to C. as a rule, and thus can be readily oxyalkylated, preferably oxyethylated, without the use of a solvent.

What has been said previously is not intended to suggest that any experimentation is necessary to determine the degree of oxyalkylation, and 75 particularly oxyethylation. What has been said SEARCH ROOlll sodium methylate as a catalyst in step-wise proportion, combines within a comparatively short time, for instance a few minutes to 2 to 6 hours, but in scmeinstance requires as much as previously is submitted primarily to emphasize the fact that these remarkable oxyalkylated resinshaving surface activity show unusual properties as the hydrophile character varies from a minimum to an ultimate maximum. One should not underestimate the utility of any of these products in a surface-active or sub-surface-active without testing them for demulsification. A few simple laboratory tests which can be conducted in a routine manner will usually give all the information that is required.

For instance, a simple rule to follow is to prepare a resin having at least three phenolic nuclei and being organic solvent-soluble. Oxyethylate such resin, using the following four ratios of moles of ethylene oxide per phenolic unit equivalent: 2 to l; 6 to l; 10 to 1; and 15 to 1. From a sample of each product remove any solvent that may be present, such as xylene. Prepare 0.5% and 5.0% solutions in distilled Water, as previously indicated. A mere examination of such series will generally reveal an approximate range of minimum hydrophile character, moderate hydrophile character, and maximum hydrophile character. If the 2 to 1 ratio does not show minimum hydrophile character by test of the solvent-free product, then one should test its capacity to form an emulsion when admixed with xylene or other insolublesolvent. If neither test shows the required minimum hydrophile property, repetition using 2 to 4 moles per phenolic nucleus will serve. Moderate hydrophile character should be shown by either the 6 to 1 or 10 to 1 ratio. Such moderate hydrophile character is indicated by the fact that the sol in distilled water within the previously mentioned concentration range is a permanent translucent sol when viewed in a comparatively thin layer, for instance the depth of a test tube. Ultimate hydrophile character is usually shown at the 15- to 1 ratio test in that adding a small amount of an insoluble solvent, for instance of xylene,

yields a product which will give, at least temporarily, a transparent or translucent sol of the kind just described. The formation of a permanent foam, when a 0.5% to 5.0% aqueous solution is shaken, is an excellent test for surface activity. Previous reference has been made to the fact that'other oxyalkylatin'g agents may require the use of increased amounts of alkylene oxide. l icwever, if one does not even care to go to the trouble of calculating molecular weights, one can simply arbitrarily prepare compounds containing ethylene oxide equivalent to about 50%.to 75% by weight, for example 65% by weight, of the resin to be oxyethylated; a second example using approximately 200% to 300% by weight, and a third example using about 500% to 750% by weight, to explore the range of hydrophile-hydrophobe balance.

A practical examination of the factor of oxyalkylation level can be made by a very simple test using a pilotplant autoclave having a capacity of about to gallons as hereinafter described. Such laboratory-prepared routine compounds can then be tested for solubility and, generally speaking, this is all that is required to give a suitable variety covering the hydrophile-hydrophobe range. All these tests, as stated, are intended to be routine tests and nothing more. They are intended to teach a person, even though unskilled in oxyethylation or oxyalkylation, how to prepare in a perfectly arbitrary manner, a series of compounds illustrating the hydrophilehydrophobe range.

If one purchases a thermoplastic or fusible resin on the open market selected" from a suitable number which are available, one might have to make certain determinations in order tomake the quickest approach to the appropriate oxyalkylation range. For instance, one should know (a) the molecular size, indicating the number of phenolic units; (17) the nature of the aldehydic residue, which is usually CH2; and (c) the nature of the substituent. With such information one is in substantially the same position as if one had personally made the resin prior to oxyethylation.

For instance, the molecular weight of the internal structural units of the resin of the following over-simplified formula:

(n21 to 13, or even more) is given approximately by the formula: (mol. wt. of phenol 2) plus mol. Wt. of methylene or substituted methylene radical. The molecular weight of the'resin would be -ntimes the value for the internal unit plus the values for the terminal units. The left-hand terminal unit of the above structural formula, it will be seen, is identical with the recurring internal unit except that it has one extra hydrogen. The'right-hand terminal unit lacks the methylene bridge element. Using one internal unit of a resin as the basic element, a resins molecular Weight is givenapproximately by taking (n plus 2) times the weight of the internal element. Where the resin molecule has only 3 phenolic nuclei as in the structure shown, this calculation will be in error by several per cent; but as it grows larger, to contain 6, 9, or 12 phenolic nuclei, the formula comes to be more than satisfactory. Using such an approximate weight, one need only introduce, for example, two molal weights of ethylene oxide or slightly more, per'ph'enolic nucleus, to produce a product of minimal hydrophile character. Further oxyalkylation gives enhanced hydrophile character. Although we have prepared and tested a large'number of oxyethylated products of the type described herein, we have found no instance where theme of less than 2 moles of ethylene oxide per phenolic nucleus gave desirable products.

The follcWin'g'Examples 1b to 10b are included to exemplify the production of suitable oxyalkylated products from resins, specifically, resins described in a number of theforegoing Examples 1a to 20a, giving exactand'complete details for the carrying out of the-procedure; We direct attention to Examples -1a to 206a andExamples 1b to 1622 and 20b to-25b of our application Serial No. 8,722 as illustrating the same matters.

Example 1b The resin employed istheacid-catalyzed paratertiary butylphenol formaldehyderesin of Example 1a. (Such resin can be purchased in the open market.) The resin is powdered and mixed with an equal weight of xylene so as to obtain solution by means of a stirringdevioe employing a reflux condenser. grams of the resin are dissolved in or mixed with 170 grams of xylene. To the mixture there is 'addedlfl grams of sodium methylate powder. The solution or suspension isplaced in an autoclave and approximately 400 CROSS REFERENCE 3? grams of ethylene oxide by weight are added in 6 portions of approximately 65 to 75grams each. After each portion is added, the reaction is permitted to take place for approximately 4 hours. The temperature employed is approximately 150 to 165 C. and a maximum gauge pressure of approximately 150 pounds per square inch. The minimum gauge pressure is approximately 20 pounds per square inch. At the end of each 4-hour period there is no further drop in pressure, thus indicating that all the ethylene oxide present has reacted and the pressure registered on the gauge represents the vapor pressure of xylene at the indicated temperature.

After the sixth and final portion of ethylene initial resin. In this instance in order to obtain,

greater solubility, the amount of ethylene oxide used for reaction was increased by a second series of additions using substantially the same conditions of reaction as noted previously. Such series was continued until, as an upper limit, 500 grams of ethylene oxide had been introduced on the basis of the original 170 grams of resin. See the attached table for data as to the compound in which the ratio of ethylene oxide to resin is about 2:1. A compound of this constitution, containing a small amount of xylene, was light amber in color, miscible with water and had a viscosity resembling that of castor oil.

Example 2b The same reactants, and procedure were employed as in Example 1b preceding, except that ylene oxide was then added, following the procedure of Example 1b, to produce products of greater hydrophile properties. We are extremely hesitant to suggest even the experimental use of glycide and methylglycide for the reason that disastrous results may be obtained even in experimentation with laboratory quantities.

Example 4b The same procedure is followed as in Example 1b except that instead of employing the resin employed in Example 1b, there was substituted instead an equal weight of resin of Example 2a. The products obtained were similar in appearance, color and viscosity to those of Example 1b.

Example 5b The same reactants and procedure are employed as in Example lb, except that the acid catalyzed amylphenol formaldehyde resin of Example 3a is used. (Such resin can be purchased in the open market.) The oxyethylated products in color, appearance, viscosity, etc., are like the products of Example 1b.

Example 6b The same reactants and procedure were employed as in Example lb, except that the acidcatalyzed styryl-phenol-formaldehyde resin of Example lie was used instead of the butylphenol resin. The oxyethylated products are similar in appearance, color, solubility, etc., to the products of Example lb.

Example 7b The acid catalyzed resin derived from parahydroxy inenthylbenzoate in the manner of Example 16a was oxyethylated. grams of this resin were dissolved in a mixture of 50 grams of xylene and 50 grams of diethyleneglycol diethylether. To this mixture was added three grams of sodium methylate. The mixture was placed in an autoclave and treated with seven successive batches of ethylene oxide. The following table tabulates the data in connection with such treatment:

Batch ggg g g f gd g Remarks as to solubility and appearance Grams Hours 0. #/sq. in. g. p.

50 4 162 88 A viscous opaque liquui; some tendency to emulsify.

5O 3 150 132 Same as before; more tendency to emulsify.

50 3 150 Viscosity of liquid reduced; tends to produce a milky emulsion.

50 3% 158 Some tendency to stratify but when mixed together was definitely water emulsifiable.

50 5 3,57 130 Non-viscous amber oilelearly homogeneous; gives a milky emulsion.

50 5 160 135 L ght colored amber 01] produces an emulsion of reduced milkiness.

50 5% 135 Light colored amber oil with even less milkiness and reasonably satisfactory solution.

propylene oxide was employed instead of ethylene oxide. The resultant, even on the addition of the alkylene oxide in the weight proportions of the previous example, has diminished hydrophile properties in comparison with the resultants of Example lb. This illustrates the point that propylene oxide and butylene oxide give products of lower levels of hydrophile properties than does ethylene oxide.

Example 3b The same reactants and procedure were followed as in Example 1b, except that one mole of glycide was employed initially per hydroxyl radical. This particular reaction Was conducted with extreme care and the glycide was added in small amounts representing fractions of a mole. Etna Example 8b The same procedure was followed as in Example lb except that the resin employed was that of Example 13a.

Example 9!) The same procedure was followed as in Example 7b except that the resin employed was that of Example 14a.

Example 10b SEARCH ROOM through amber, to a deep red :or even :almost black. In the manufacture ,ofresins, particularly hard resins, as the reaction'progresses the "reaction mass frequently goes through a liquid state to'a sub-resinous or semi-resinous state, often characterized by .being'tacky or sticky, to a final complete resin. As 'the resin is subjected to oxyalkylation these same physical changes tend to take place in reverse. If one starts with a solid resin, oxyalky-lation tends to make it tacky or semi-resinous and further oxyalkylation makes the tackiness disappear and changes the product to a liquid. Thus, as the resin is oxyalkylated it decreases-in viscosity, that is, becomes more liquid or changes from a solid to a liquid, particularly when it is converted to the waterdispersible or water-soluble stage. The color of the oxyalkylated'derivative is usually considerably lighter than the original product from which it is made, varying from a pale straw color to an amber or reddish amber. The viscosity usually varies from that of an oil, like castor oil, to that of a thick viscous sirup. Some products are waxy. The presence of a solvent, such as xylene or the like, thins the viscosity considerably and also reduces the color by dilution. No undue significance need'be attached to the color for the reason that if the same compound is preparedin glass and in-iron, the latter usually has somewhat darker color. -If the resins are prepared as customarily employed in varnish resin manufacture, i. e., a procedure that excludes the presence of oxygen during the resinification and subsequent cooling of the resin, then of course the initial resin is much lighter in color. We have employed some'resins which initially are almost water-white and also yield a lighter colored final product.

The same procedure as described above has been applied to a'large variety of resins ofthe kind described previously, including resins'obtained from mixtures of phenols, and we have found that these oxyalkylated products having the required minimum hydrophile properties, are all effective for use in the process of the invention. In many cases resins used were obtained from aldehydes other than formaldehyde, 1. e., higher aldehydes having not over 8 carbon atoms. Similarly, some of the resins instead of being obtained by us'e'of acid catalysts were'obtained by use of alkaline catalysts or sequential use of both types of catalyst. In some instances the resins were obtained by a process'which involved a secondary step of heating alone or under vacuum. In the series of examples represented by Example 1b throughlOb and the examples of ap plication Serial No. 8,722, the amount of alkylene oxide added covers the range up-toabout three times the weight of the initial resin. In our application Serial No. 8,722 there is a table which illustrates the effect of oxyalkylation of a wide range of phenolic resins, and show'that many efiective compounds for demulsification purposes require but about one-half this amount of alkylene oxide compound, in particular ethylene oxide, for example'froni 156% to'200% by weight. Of the products illustrated in the table'in said application Serial No. 8,722, those derived from products illustrated by Examples 1a to 206a of that application are useful for the practice of the present invention andillustrate zit. Larger amounts of ethylene oxide, for examplaamoun'ts up to six times the weight of the initial resinmay be used, even though the solubility of-such productsmany in some cases be less than the solu- B. S. 8: W. content was lessthan of 1%.

d0 bility ofi derivatives obtained withlesser amounts of alkylene oxide.

The oxyethylated products, in the presence of the solvent; were liquids varying in viscosity from relative mobility to' a viscosity approaching that of castor oil or lightly blown vegetable oils. They varied in color from straw colored or light amber to very dark brownish or reddish colored. It is to beunderstood that when these products are used for demulsification, it is unnecessary to separate them from the solvent used in their preparation, and ordinarily commercial products will, if preparedwith the use of a solvent, be distributed without removal of the solvent, and frequently with the addition of othersolvent materials other agents, etc.

The following examples, Examples 10 to 3c, are included to illustratethe technique of testing the effectiveness of the demulsifiers against oil field emulsions. It is to be understood that in the industrial use of these products, they are used in accordance with standard practices, some of which are subsequently described.

Example 1c The demulsifier employed was the oxyalkylated derivative ofthe resin of Example 2a'prepared from para-secondary butylphenol and formaldehyde using an acid catalyst oxyethylated with an amount of ethylene oxide equal in weight to the weight of the resin, followin the procedure of Example 4b.

The oxyalkylated resin was prepared so the final product represented a 50% solution in xylene. The eifectiveness of this oxyalkylated resin was examined by testing it in connection with an emulsionpro'duced at the St. Gabriel field, St. Gabriel, Louisiana. The emulsion as produced was loud in color and contained approximately 70% to.80% B. S. & W., equivalent to 40% water. The oxyalkylated derivative above described was added to 100 cc. of emulsion'placed'in a 150 cc. bottle. The amount added was equivalent to one part of demulsifier in 25,000 parts of emulsion. The mixture was shaken for three minutes in a shaking machine employing 150' oscillations per minute. The emulsion began to changecolor at the end of one minute, completely changed color at the end of two minutes, and was obviously breaking, even during the agitation period, by the end of the third minute. At-the end of ten minutes of quiescent settling, a distinct water layer had broken out. The emulsion was allowed to stand for one hour at approximately to F. All the water was broken out within less than the hour, giving a clear separation. The gravity of the recovered oil was 34 A. 'P. I., and the In large scale :use it is not necessary to get a complete resolution Within an hours time and the amount of demulsifier required would be substantially less.

Example 20 Thedemulsifier employedwas the oxyalkylated derivative-of the resin of Example 3a prepared from para-tertiary amylphenol and formaldehyde, using an acid catalyst, oxyethylated with an amount of ethylene oxide equal in weight to the weightof the-resin following theprocedure of Example 5b.

The oxyalkylated resin was prepared so the finaljproduct represented a 50 solution in Xylene. The "efiectiveness'of this oxyalkylated resin was 75 examined bytesting itxin connection withan 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING A HYDROPHILE OXYALKYLATED 2,4,6 SUBSTITUTED MONOCYCLIC PHENOL C1- TO C8- ALDEHYDE RESIN IN WHICH THE RATIO OF OXYALKYLENE GROUPS TO PHENOLIC NUCLEI IS AT LEAST 2:1 AND THE ALKYLENE RADICALS OF THE OXYALKYLENE GROUPS ARE SELECTED FROM THE GROUP CONSISTING OF ETHYLENE, PROPYLENE, BUTYLENE, HYDROXY PROPYLENE AND HYDROXY BUTYLENE RADICALS. 